Textile materials treated with a linear polymeric ester



nited States Patent '"ce ciiiiiii a meric esters have a wide range of compatibility with other 3,134,332 textile finishing agents and exhibit a synergistic effect TEXTILE A LINEAR with creaseproofing compositions to give a higher crease P recovery angle than that obtainable with the creaseproofing Michael R. Rachinsky, East Rutherford, N.J., assignor to t D L 0 5 composition alone. 2:55: 3? ggggg g W1 mmg e a c The linear polymeric esters represented by the above No Drawing. Filed Mar. 1, 1963,Ser.No.262,180 formula are polyesters having a plurality of OH sub- 7 Claims. (Cl. 117-139.4) stituent groups attached at regular intervals along the polymer chain and which may or may not be end termi- This invention relates to textile fabrics having uni- 10 nated. The most preferable polymeric esters are those formly distributed therethrough linear polymeric esters having the following general formula:

0 0 0 g P I g l g RCHCH[CH7]r- -O I ''OH[C 2]n O- (B -OHICHz]n -OW -CH H 0 l l R x R and to the treatment of textile fabrics with linear polyin which R is a substituent of the group consisting of meric esters to improve the properties thereof. hydrogen and alkyl radicals; n is a whole number from The incorporation of polymers into textile materials 0 to 20, inclusive; x is at least 1; and W is a substituent to impart such desirable properties as abrasive resistance, 0f the group consisting of hydrogen, hydroxyalkyl radia soft hand, tear and/ or tensile strength, or irnpermeabilcals and halohydroxyalkyl radicals. ity to certain solvents, is well known. However, the The linear polymeric esters used in this invention are treated textile materials of the prior art all suffer certain prepared by heating epoxyalkanoic acids or the alkali disadvantages. Some fabrics, as for example those treated metal salts of halohydrated saturated aliphatic acids.

with natural rubber latex, have a rubbery hand, i.e., a rub- Exemplary epoxyalkanoic acids are bery feel when the fabric is handled. Other fabrics, such as those treated with polyvinyl acetate, polyvinyl chlo- 133i ride and certain copolymers of vinyl acetate and vinyl z3 epoxyhexanoic i chloride have a papery hand, i.e., the fabric has a crisp, s4 epoxyhexanoic acidf brittle feel and conveys the impression of thinness and 56 epoXyheXanOic acidf fragility. In still other fabrics, the prior art treating z3 epoxyoctanoic acidj compositions produce color, lack of strength, or are octanoic acidf washed away by solvents. Still another disadvantage is 7s epoxg;octanoic the fact that some prior art polymeric treating agents 23 epoxyundecanoic acid. are incompatible with conventional textile finishing agents. s6 epoxyundecanoic It has now been found that textile fabrics having unib ED oxyun decanoic 6 formly distributed therethrough a polymeric substance zepoxyhexadecanoic acidf comprising at least 0.5% by weight (based on the fabric) 78 ep0XyheXadeCanOic acid: of a linear polymeric ester having the following general 15,16 ep oxyhexa d6 canoic orm 2,3-epoxyoctadecanoic acid;

in which R is a substituent of the group consisting of 9,10-epoxyoctadecanoic acid; hydrogen and alkyl radicals; n is a whole number from 10,11-epoxyoctadecanoic acid; 0 to 20, inclusive; x is at least 1; B is a substitutent of 11,12-epoxyoctadecanoic acid; the group consisting of 12,13-epoxyoctadecanoic acid; n-orr-orrradicals, mon-orrradicals, RCH- CH-radicals' l7als'epoxyoctadecanoic acid; 6110' 0 X 11 Exemplary halohydrated saturated aliphatic acids are t) 0 H H 2(3)-chloro-3(2)'hydroxybutyric acid; YCO-CH- radicals, and YC--O-C-C radicals y y Y acid; f I 2(3)-iodo-3 (2)-hydroxyhexanoic acid;

Eu|JOH 3 (4)-chloro-4 3 -hydroxyhexanoic acid; R 5 (6)-chloro-6(5 )hydroxyoctanoic acid;

in which R has the same significance as set forth above, (7)- y xy n i acid; X is a halogen substituent, and Y is a substituent of the Y l/ acid; group consisting of hydrogen, straight and branched chain y y x n i acid; aliphatic hydrocarbon radicals, )t;1 (1l53-hydroxyhexadecanoic acid;

3 -c oroy roxyoctadecanoic acid; R CH mhcals and R CH CH radicals 9( lO)-chloro-l0(9)-hydroxyoctadecanoic acid;

OH OH OH 10(1l)-chloro-l1 (10)-hydroxyoctadecanoic acid; in which R has the same significance as set forth above; ll(12)-chloro-12(l1)-hydroxyoctadecanoic acid; and Z is a substituent of the group consisting of hydrogen, 12(13)-chloro-13(l2)-hydroxyoctadecanoic acid;

hydroxyalkyl radicals, halohydroxyalkyl radicals, and l7(18)-bromo-l8(l7)-hydroxyoctadecanoic acid; etc.

alkali metal radicals exhibit a soft hand which cannot The polymerization involves the reaction of epoxy or easily be washed away and are not discolored by househalohydrin substituent groups with carboxylic acid hold bleaches and detergents. The above-defined polysubstituent groups of adjacent molecules to build up the rtors to the polymerization mixture.

3 linear polymeric ester structure, and can be conducted with or Without a basic catalyst. In general, acids with internal epoxy groups react somewhat slower than acids having terminal epoxy groups.- For example, 10,11- epoxyundecanoic acid starts polymerizing without a catalyst in solution at temperatures slightly above room temperature, whereas 9,10-epoxystearic acid requires temperatures in excess of 100 C. to start polymerizing. The polymerization of epoxyalkanoicacids is preferably con ducted in the presence of a basic catalyst and at temperatures between about 75 C. and about 200 C. Suitable basic catalysts include by way of example, alkalirrnetal oxides and hydroxides, alkali metal alcoholates,- alkali metal salts of the epoxyalkanoicacid or acids being polymerized, as well as Lewis bases, such as triethylenediamine. These catalysts can be used in concentrations from about 0.01% to about 5% by weight, based'o'n the 7 weight of epoxyalkanoic acid.

A catalyst is neither necessary nor required when alkali metal salts of halohydrated saturated aliphatic acids are polymerized, heat alone being sufiicient to effect polymerization at temperatures between about 75 C. and about samples at intervals, and .analyzing for acid number, saponification number or oxirane oxygen content when an epoxyalkanoic acid is being polymerized and ester number. when an alkali metal salt of a halohydrated saturated aliphatic acid is being polymerized.

The simplest means for controlling the degree of polymerization of these polymers is by just stopping the polymerization, i.e., discontinuing the heating of the reaction mixture when analysis indicates that the desired degree of polymerization has been reached. However, polymerization can also becontrolled byadding chain termina- Various types of chain terminating agents can be'used dependingupon the specific polymerization being'controlled. Monofunctional polyoxyethylene ethanol, polyoxyethylene lauryl alcohol, etc. The emulsions can then 'be stripped of the organic solvent or solvents by steam distillation to give a dilute dispersion which can be concentrated by further distillation or by other known methods if desired. Dispersions having various total solids composition can be prepared. In general, however, the latices will have a total solids content of at least about 0.5% by weight.

The textile material can be treated with the polymeric ester dispersion in a number of ways, for example, the material can be saturated by dipping or running a continuous belt of the material through a trough of the dispersion; The dispersionxcan also be applied to the material by spray, foam or knife-coating techniques. Still other methods of applying the dispersion will be apparent to those skilled in the art.

The amount of polymeric ester employed will embrace a wide range of proportions depending upon the specific textile material being treated, the specific polymeric ester being employed, and the properties'desired in the finished fabric. In general, the amount of polymer employed in the treatment of the material-will be sufiicient to yield a fabric containing from about 015% to about 5.0%, more preferably from about 1.0% to about.2.0%, of the polymeric substance by weight. The amount of polymer' in the fabric can also be expressed'as percent add-on,

which is the percent increase in the weight of the fabric epoxides such as alkylene oxides and epihalohydrins,-ali-' phatic acids, hydroxy aliphatic acids and dihydroxy aliphatic acids can be used when polymerizing epoxyalkanoic acids. The alkali metal salts of aliphatic acids, hydroxy aliphatic acids, and dihydroxy aliphatic acids can beused when polymerizing halohydrated alkanoic acids.

Any textile material can be treated with a polymeric composition containing a linear polymeric esterin accordance with the process of this invention; Exemplary of the various textile materials are those containing either b-amates, formaldehyde, methylolureas,etc.

due to the addition of the polymeric substance.

Various auxiliary modifiers, such as dyes, including the V anionic dyes, pigments, fillers, water-miscible waxes, resins, shrinkproofing agents, creaseproofing agents, etc., can be employed as desired depending upon the use to which the product is to be put. The use of linear polymeric esters with creaseproofing compositions is particularly advantageous. since 'a higher crease'recovery angle is obtained than can be'obtainedwith a creaseproofing composition. alone. Examplary of thecreaseproofing compositions which can be employed in accordance with this invention are melamine-formaldehyde resins, 1,3- b1s[2 (3 hydroxymethyl-Z-imidazolidinon-1-yl)ethyl]- 1,3 bishydroxymethylurea, diepoxides, disulfones, dicar- Obviously there are many cases in which an auxiliary modifier is not a required or desired and excellent results are achieved natural or synthetic fibers, such as cellulose, wood, jute, V

sisal, ramie, hemp, manilla, wool, silk, and cotton, as well as fibers or filaments of rayon, those cellulose esters such as cellulose acetate, the polynosic rayon fibers such as resin fibers such as those of poly(.vinyl chloride), copolythat marketed under the trade name of Zantrel, vinyl mers of vinyl chloride .with' vinyl acetate, vinylidene I of the nylon type, polyesters such as poly(ethylene terephthalate) and the. like. I

The linearrpolymeric esters are preferably'employed as aqueousdispersions; however, solutions of the polymers can alsobe used. The aqueous dispersions'can be prepared by any of a number of procedures. One convenient procedure is to prepare a solution of the linear polymeric ester in an organic solvent andthen form an emulsion by mixing with water and a small amount of surface active agent, i.e., the ,nonionic agents suchas polyoxyethylene sorbitan monolaurate, methyl phenoxyotherwise specified.

without them.

If a creaseproofing or shrinkproofing agent is used, the

treated fabricis generally heat treated toYset the agent.

This heat treatment can be accomplished in any suitable manner. A simple method is to remove excess aqueous dispersion by passing the material through nip rollers at about 20 p.s.i. and thendry and heat 'on a drum drier at a temperature of from about C. to about 185 C.

The following examples'are presented for purposes of illustration, parts and percentages being by weight unless EXAMPLE 1 This example illustrates the preparation of a linear polymeric ester of anep'oxy alkanoic acid and its end termination. V

" Amixture of 575 parts by weight of .9,10.-epoxystearic acid, of 78% purity, and 1.5 parts by weight of triethylenediamine was heated in'a closedpolymerization vessel in a nitrogen atmosphere at 180 C. for one hour, then 63.5 parts by weight ofrepichlorohydrin was injected into the reaction, 'After maintaining the mixture at a temperature of C; for another hour, the excessepichlorohydrin was removed. The resulting product was a heavy oil having .an acid number of 1.2, an ester number of 221.4

'and a hydroxyl number of 167.1.

7 EXAMPLE 2 An aqueous dispersion was prepared from the polyester of Example 1 as: follows: To a 10% solution of the polymeric ester in acetone was added 10% (based on the weight of the polymeric ester) of polyoxyethylene sorbitan monolaurate and 1 part of warm water per part of polyester. The emulsion Was vigorously agitated and then the acetone was steam stripped to give a dispersion having a total solids content of 65%. The dispersion was diluted with water to a 1% total solids content and used to treat a sample of SO-square cotton broadcloth. The sample of broadcloth was saturated by dipping in the latex, put through a nip roll at 20 p.s.i. and air dried. The thus treated cloth was then dipped into a 6.8% aqueous solution of a commercial acetal creaseproofing resin containing 1% of magnesium chloride based on the weight of the resin. The sample was dried at room temperature and then cured for 1 minute on a drum drier at a temperature of 177 C. The thus treated cloth had a soft lasting hand. It had a 1% add-on by Weight of the polymeric ester and a 6% add-on by weight of the acetal resin. After five launderings, the treated sample was tested and found to have a crease-recovery angle of 241", a dry-warp tensile strength of 27 lbs. per inch and a drywarp tear strength of 2.1 lbs. An untreated sample of the broadcloth had a crease-recovery angle of 170.

EXAMPLE 3 An aqueous dispersion was prepared from a propylene oxide-terminated poly(9,10-epoxystearic acid) having an ester number of 188.6 and a hydroxyl number of 179.4 exactly as described in Example 2. The resulting concentrated dispersion was diluted with water to a 1% total solids content and sufiicient commercial acetal creaseproofing resin was added to amount to 6% of the dispersion. A sample of 80-square cotton broadcloth was saturated by dipping in the dispersion, put through a nip roll at 20 p.s.i. and air dried. The sample was then cured for 2 minutes in a circulating air oven at a temperature of 177 C. The thus treated cloth had a soft lasting hand. After five launderings, the sample was tested and found to have a crease-recovery angle of 250, a dry-warp tensile strength of 28 p.s.i. and a dry-warp tear strength of 2.2 lbs. An untreated sample of the broadcloth had a crease-recovery angle of 170.

EXAMPLES 46 Three aqueous dispersions of polymeric esters were prepared following the method described in Example 2. In each dispersion of surface active agent, based on the weight of the polymeric ester, was used. The polymeric esters and surface active agents used and the solids content of each dispersion is listed below.

EXAMPLE 4 Polymeric ester.-Poly(9,10-epoxystearic acid) having an acid number of 84.4, an ester number of 128 and a residual oxirane-oxygen content of 0.76%.

Surface active agent.-An alkyl phenoxypolyoxythylene ethanol, 59.5% total solids.

EXAMPLE 5 Polymeric ester.Poly(9,l0-epoxystcaric acid) terminated with epichlorohydrin having an acid number of 1.2, an ester number of 221.4 .and a hydroxyl number of 167.1.

Surface active agem.-A polyoxycthylene sorbitan monolaurate, 65% total solids.

EXAMPLE 6 Polymeric ester.-Poly(9,10-epoxystearic acid) having an acid number of 44.

Surface active agcnt.A polyoxyethylene lauryl alcohol, 61.1% total sol-ids.

Each dispersion was diluted with water to a 1% total solids content and used to treat individual samples of 80-square cotton broadcloth. Each sample of cotton broadcloth was saturated by dipping in a dispersion, put through a nip roll at p.s.i. and air dried. Each cloth The pH of this dispersion was adjusted to 8.5 with armmonium hydroxide.

was then dipped into a 10% solution of a commercial thermosett-ing, nitrogeneous, cyclic methylol resin, precursor, creaseproofing agent containing 5% of ammonium sulfate based on the weight of the resin. Each sample was dried at room temperature, then cured for 1 minute on a drum drier at a temperature of 177 C. The thus treated samples possessed a soft hand and had not changed in color. The percent add-on of polymeric ester and creaseproofing agent and some properties of the treated samples and an untreated control sample are shown in Table I.

Table I Poly- Crease- Crease-recovery Tensile, Trapemer proofing Angle, degrees p.s.i. zoid Examples Add- Agent Tear, On, Add-On, Lbs. perpercent Un- After 5 Dry Wet dry cent washed washes EXAMPLE 7 A sample of -squ-are cot-ton broadcloth was treated with a dispersion of epichlorohydrin-terminated poly(9,10- epoxystearic acid) containing a commercial epoxy creaseproofing agent. The dispersion was exactly the same as the dispersion of Example 5, except for the addition of the different creaseproofing agent. A control solution of the creaseproofing agent alone was prepared. Individual samples of 80-square cotton broadcloth were dipped into the dispersion and control solution. Each sample was then put through a nip roll at 20 p.s.i. and air dried. The thus treated samples were cured for 3 minutes in an air circulating oven at a temperature at 163 C. The cloth sample treated with the dispersion containing epichlorohydrin-terminated polymer possessed a soft lasting hand while the sample treated with creaseproofing agent alone did not exhibit a soft hand.

EXAMPLE 8 A sample of SO-square cotton broadcloth was treated with a creaseproofing agent and the aqueous dispersion of Example 5 as follows: The cloth was first treated with an aqueous solution of 1,3 bis[;2-(3 hydroxymethyl-2- imidazolidinon-1-yl)=ethyl] 1,3 bis hydroxymcthylurea containing 5% ammonium sulfate based on the weight of the urea compound. The cloth was put through a nip roll at 20 p.s.i. and air dried. The percent add-on of urea creaseproofing agent was 8.4%. The cloth was then treated with the dispersion of Example 5, put through a nip roll at 20 p.s.i. and air dried. The percent add-on of epichloro'hydrin terminated poly-(9,10 epoxystearic acid) was 2.0%. The thus treated cloth was cured for 5 minutes in a circulating air oven at a temperature of 149 C. The treated cloth had a soft hand and a creaserecovery angle of 309.

EMMPLE 9 This example demonstrates the treatment of woolen blanket material with a shrinkproofing agent and aqueous dispersion of an epichlorohydiin terminated poly(9,10- epoxystearic acid) having an acid number of 0.3, an ester number of 224.3 and a 'hydroxyl number of 69.5. The dispersion was prepared as described in Example 2. The dispersion was diluted with water to 2% total solids and sufficient epichlorohydrin-modified am-inopolyamide resin was added to amount to 7% of the dispersion. A sample of the Woolen material was dipped into the dispersion, put through a nip roll at 20 p.s.i. and air dried. The percent add-on of the epichlorohydrin-terminated polymeric ester was 2% and of the polyam'ide resin, 7%. The material was then cured for 75 minutes in a circulating air oven at a temperature of 149 C. The thus treated material possessed a soft lasting hand and was essentially shrinkproof.

EXAMPLE A dispersion was prepared exactly as described in Example 9 and then diluted with water to 2% total solids. To the dilute dispersion was added sufiicien-t epichlorohydrin-mod ified aminopolyamide nesin to amount to 2% V in which R is a substituent of the group consisting of hyof the dispersion plus 0.04% sodium bisulrfite based on,

the weight of the resin. The pH of the dispersion was then adjusted to 6.8 by the addition of sodium hydroxide; A sample of 16 oz. wool serge was dipped into the dispersion and put through. a, nip roll at p.s.i. 'The treated cloth was then creased and pressed with a steam iron to dryness. The thus treated cloth possessed asoft lasting hand and a permanent crease. The cloth was tested .by boiling in water for 1 hour and in perch-loro ethylene for 1 hour. perceivable change.

. EXAMPLE 11 An aqueous dispersion was preparw from a nonterrni It withstood the treatment with no nated p'oly(9,lO-epoxystearic acid) having anaci-d uum,

ber of 75.3, and oxi'r-ane-oxygen content of 1.34% by weight and an equivalent weight of 286.5 exactly as described in Example 2. The resulting concentrated dis.

'persion was diluted with water to a 1% total solids content. A sample of SO-square cotton broadcloth was saturated by dipping in the dispersion, put through a nip 7 roll at 20 p.s.i., and air dried. The thus treated cloth had a soft hand even after repeated launderings.

. EXAMPLE 12 An aqueous dispersion was prepared from a propylene oxide terminated po1y(10,11-epoxyundecanoic acid). having an acid number of 1.5, an oxirane-oxygen content of 0.2% by Weight and an ester number of 216 by the method described in Example 2 except that in place of the polyoxyethylene sorbitan monolaurate surface active agent was substituted polyoxyethylene lauryl alcohol. The resulting concentrated dispersion was diluted with water to a 1% total solids content and suflioient commercial acetal creaseproofing resin was added to amount to 6% of the dispersion. A sample of SO-square cotton broadcloth was saturated by dipping in the dispersion, put througha nip roll at 20'p.s.i. and air dried. .The sample was then cured for 2 minutes in a circuiating air oven at a temperature of 172 C. The thus treated cloth had a soft lasting hand. After five launderings thle sample was tested and found to have a crease-recovery angle of 275. A control sample of the broadcloth treated with the creaseproofing agent alone had a creaserecovery angle of 204? after five launderings. r

What I claim and desire to protect by Letters Patent 1. As an article of manfuacture, a textile fabric having uniformly distributed therethrough a polymeric substance comprising at least 0.5% by weight (based on the fabric) of a linear polymeric ester having the general formula:

drogen and alkylradicals containing from 1 to 15 carbon atoms; n is a whole number from 0 to 20, inclusive; x is at least 1; B isia substituent ofthe group consisting of IL -CE-CH-radicals, R(|3 H O lELradieals, R. C I-I O I-I-radicals in which R has the same significance as set forth above,

uniformly distributed therethaough a polymeric substance comprising at least 0.5 by Weight (based on the fabric) of a'linear polymeric ester having the general formula:

in which R is a substituent of the group consisting of hydrogen and alkyl radicals containing from 1 to 15 carbon atoms; nis a Whole number from 0 to 20, inclusive;

0c is at least 1; and W- is a substituent of the group consisting of hydrogen, hydroxyalkyl' radicals containing from 1 to 15 carbon atoms and halohydroxyalkyi radi- 40 'cals containing from 1' to 15 carbon atoms.

3. An article of:m=anufacture as in claim 2 wherein the linear polymeric ester is an ester of 9,10-epoxystearic acid. i

4. Anfa'rticle of manufacture as in claim Z-Wherein the linearpolymeric ester is an epich'lorohydrimterminated ester of 9,10-ep-oxystearic acid.

5."An article of manufacture as in claim2 wherein the linear polymeric ester is a propylene oxide-terminated ester of 9,10 epoxystearic acid.

6. An article of manufacture as in claim 2 wherein the polymeric substance is a mixture of.poly(9,10-epoxystearic acid) andacreaseproofing agent selected from the group consisting of melamine-formaldehyde resins, 1,3 bis[2 (3 hydroxymethyl 2 -irnidazolidinon 1 y1-)ethyl] 1,3 bishydroxymethylu-rea, diepoxi des, di sulfones, dicarbamates, formaldehyde'and methylolureas. 7. An article of manufacture as in claim 2 wherein the polymeric substance is amixture of epichlorohydrin-terminated poly(9,10-epoxystearic acid) and a oreaseproofing agent selected from the group consisting of melamineformaldehyde resins, 1,3 bis[2 (3 hydroxymethyl 2 imidazolidonin 1 yl) ethyl] 1,3 bishydroxymethyl urea, diepoxides, disulfones, dicarbamates, formaldehyde and methylolureas.

References Cited by the Examiner UNITED STATES PATENTS 2,567,237 9/63 Scanlan et al. 260- 348 WILLIAM D. MARTIN, Primary Examiner. RICHARD D. NEVIUS, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,184,332 May 18, 1965 Michael R. Rachinsky It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 42 to 47, the formula should appear as shown below instead of as in the patent:

column 2, lines 12 to 15, the formula should appear as shown below instead of as in the patent:

H CH2 c-0 OH [I n column 7, lines 65 to 70, the formula should appear as shown below instead of as in the patent:

column 8, lines 5 to 7, the second formula should appear as shown below instead of as in the patent:

R-CH-CH-radicals,

X OH

same column 8, lines 29 to 33, the formula should appear as shown below instead of as in the patent:

0 o I H u R-CH-CH-[CH 1 l-o CH [CH -c-o H -[CH -c-ow \J 2 n I EILOH 2 n OH 2 n -cl:H -(IIH R R Signed and sealed this 7th day of December 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. AS AN ARTICLE OF MANUFACTURE, A TEXTILE FABRIC HAVING UNIFORMLY DISTRIBUTED THERETHROUGH A POLYMERIC SUBSTANCE COMPRISING AT LEAST 0.5% BY WEIGHT (BASED ON FABRIC) OF A LINEAR POLYMERIC ESTER HAVING THE GENERAL FORMULA: 